Halohydrin thioethers and method of preparation

ABSTRACT

COMPOUNDS OF THE STRUCTURE R(SCH2CHOHCH2X)N WHEN N=1 TO 4 AND R IS A HYDROCARBON, ETHER, ESTER, ACETAL, HYDROXY ALIPHATIC, HYDROXY AROMATIC, IMIDE OR AMIDE GROUP OR HALOGENATED DERIVATIVES THEREOF ARE PREPARED BY REACTING 1-HALO-3-MERCAPTO-2-PROPANOL WITH AN ALIPHATICALLY UNSATURATED COMPOUND USING FREE RADICAL INITIATORS AS CATALYSTS. THE COMPOUNDS IN WHICH R IS AN UNSATURATED ALIPHATIC HYDROCARBON GROUP OF 2 TO 24 CARBON ATOMS, OR AN UNSATURATED CYCLOALIPHATIC GROUP, AND THOSE IN WHICH THE ALIPHATIC OR CYCLOALIPHATIC GROUP IS CONNECTED TO TWO OR MORE -S-CH2CHOHCHCL GROUPS, AND COMPOUNDS WHERE R IS AN ALKYLENE SUBSTITUTED AROMATIC GROUP AND HYDROXY, THIOALKYL, ALKOXY, ARYLOXY, ESTER, CARBAMIDOALKYL AND SULFAMIDOALKYL, HALOGENATED DERIVATIVES OF SAID GROUPS ARE NEW COMPOUNDS. THE THIOETHER HALOHYDRINS CAN BE CONVERTED TO EPOXIDES. THE PROCESS UTILIZING A RADIOACTIVE ENERGY SOURCE AS A CATALYST IS NEW.

United States Patent Olfice 3,784,607 HALOHYDRIN THIOETHERS AND METHODOF PREPARATION Richard A. Hickner and Corwin J. Bredeweg, Midland,

Mich., assignors to The Dow Chemical Company, Midland, Mich.

No Drawing. Original application Oct. 3, 1968, Ser. No. 764,956, nowabandoned. Divided and this application Aug. 9, 1971, Ser. No. 170,302

Int. Cl. C07c 149/18 US. Cl. 260-609 R Claims ABSTRACT OF THE DISCLOSURECompounds of the structure R(SCH CHOHCH X) when n =1 to 4 and R is ahydrocarbon, ether, ester, acetal, hydroxy aliphatic, hydroxy aromatic,imide or amide group or halogenated derivatives thereof are prepared byreacting l-halo-3-mercapto-2-propanol with an aliphatically unsaturatedcompound using free radical initiators as catalysts. The compounds inwhich R is an unsaturated aliphatic hydrocarbon group of 2 to 24 carbonatoms, or an unsaturated cycloaliphatic group, and those in which thealiphatic or cycloaliphatic group is connected to two or more -SCHCHOHCHCl groups, and compounds where R is an alkylene substitutedaromatic group and hydroxy, thioalkyl, alkoxy, aryloxy, ester,carbamidoalkyl and sulfamidoalkyl, halogenated derivatives of saidgroups are new compounds. The thioether halohydrins can be converted toepoxides. The process utilizing a radioactive energy source as acatalyst is new.

This application is a division of our prior application Ser. No.764,956, filed Oct. 3, 1968 for New Halohydrin Thioethers and Method ofPreparation, now abandoned.

SUMMARY OF THE INVENTION This invention relates to novel thioethershaving vicinal --OH and halogen groups and to methods of manufacture ofhalohydrin thioethers by reacting a halohydroxy thiol with a compoundhaving alicyclic or aliphatic carbon-to-carbon unsaturation. Moreparticularly, the invention pertains to methods of making thioethers ofthe structure R(-S-CH CHOHCH X),,, where R is a hydrocarbon, ether,ester, acetal, alcohol, imide or amide group or a halogenated derivativethereof, n is an integer of 1 to 4 inclusive and X is chlorine orbromine, and to certain novel compounds of the above generic structure.The thioethers are prepared by reacting l-halo- 3-mercaptopropanol-2with a compound having aliphatic carbon to carbon unsaturation in thepresence of a free radical initiating catalyst. The reaction iseffective with monoolefinic compounds, which form derivatives with asingle S--CH CHOHCH X group and polyolefinic compounds, to formderivatives with a plurality of -SCH CHOHCH X groups and with acetyleniccompounds where one to two SCH CHOHCH X groups are added to eachacetylenically unsaturated group.

Each new compound has at least three reactive sites in that the halogenis labile and can be hydrolyzed under proper conditions to form thecorresponding glycol, each can be esterified with carboxylic acidanhydrides to convert the OH to an ester group or each can bedehydrohalogenated to form an epoxide. The epoxides can be polymerizedby known procedures to form homopolymers from single compounds andcopolymers from mixtures of epoxides. The epoxides are stabilizers forvinylidine chloride homopolymers and copolymers of vinyl and vinylidenechlorides with other monoolefinically unsaturated monomers. Forstabilizing the vinyl and vinylidene chloride-containing homopolymers orcopolymers,

Patented Jan. 8, 1974 concentrations of 1 to about 5% by weight of theepoxide based on the weight of the polymers is usually sufficient. Theepoxides are also useful for treating textiles having active H atoms,such as cellulose, to provide improved crease resistance.

The prior art processes for preparing halohydrin thioethers used Lewisacids, such as zinc chloride, to catalyze the reaction between anepihalohydrin and a mercaptan. These catalysts also elfectpolymerization of the epihalohydrins, which resulted in poor yields ofdesired derivatives and made separation of desired compounds quitedifficult. Other processes known to the art all require a mercaptan as astarting material. Many of the mercaptans are not readily accessible.

It has now been found that a wide variety of new and useful halohydrinthioethers can be prepared simply and in good yields, Without undueby-product formation. Another advantage is that one small class ofhalomercaptopropanols can be reacted with a very wide variety of readilyavailable alicyclically or aliphatically unsaturated compounds to formhalohydrin thioethers.

Another advantage is that it is possible to form compounds having amultiplicity of SCH CHOHCH X side groups.

A further advantage is that when radiation catalysis is employed, noextraneous ingredients are added to the reaction mixture.

The sulfur atom of the RSCH CHOHCH X compounds is always attached to analiphatic group of at least 2 C atoms, or to a saturated cycloaliphaticring. Thus, R in the generic structure represents an aliphatichydrocarbon group of from 2 to 18 C atoms, an alkoxyalkyl, apolyoxypolyalkenyl, alkylcarboxy, alkylcarboxyethyl, an alkenyl, analkylcarbamidoalkyl, a hydroxyalkyl, an aralkyl, aralkoxy, aroxyalkyl,arylcarboxyalkyl, arylcarbamidoalkyl, alkylcarbamidoalkyl,hydroxyaralkyl, hydroxyaroxyalkyl, cyclohexyl, cyclooctenyl,cyclohexylalkyl and bridged polynuclear terpene residue, halogensubstituted derivatives of said groups and a tetrahydrofurfuryl orpyrrolidinyl nucleus.

Compounds in which R is alkenyl, haloalkyl, haloalkenyl, alkylcarboxy,alkoxyalkyl, polyoxypolyalkenyl, alkylcarboxyalkyl, alkylcarbamidoalkyl,alkylcarbamidoalkyl, and all the aromatic ring containing groupsrepresent new compounds of this invention.

Both olefinic and acetylenic groups react with thel-halo-3-mercapto-2-propanols to form monoadducts with monoolefins, monoand diadducts with acetylenic linkage and mono and polyadducts withpolyolefinically unsaturated compounds.

Although the invention is exemplified by reactions of relatively purecompounds, it is to be understood that mixtures of olefinically and/oracetylenically unsaturated compounds can be reacted with thehalomercaptopropanol to form a mixture of adducts.

The reaction can be effected at any temperature where the individualreactants are liquid. In cases where one reactant is gaseous at roomtemperature, the reaction can be carried out under sufiicient pressureto liquify the gaseous ingredient or at a temperature low enough toli-quify the gas. In certain instances, it may be most desirable tocarry out the reaction in a common solvent which is nonreactive witheither the unsaturated compound or the halomercaptopropanol and whichhas a low freezing temperature. A common solvent of the above-describedtype may also be desirable with some unsaturated compounds which aresolid at reaction temperature. Typical solvents are the lower alkanolsof from 1 to about 6 C atoms, liquid alkanes and hydrocarbons havingonly aromatic unsaturation and halogenated derivatives of suchhydrocarbons.

The reaction can be carried out at temperatures ranging from about 50 C.to about 150 C. The reaction rate, however, is usually sufiicientlysatisfactory at 25 to 80 C. and therefore this range is preferred.

The free radical initiators that can be employed include azo compounds,examples of which are azobisisobutyronitrile and azobisisobutyric acid,carboxylic acid peroxides such as benzoyl peroxide, ring halogenatedderivatives thereof, caprylyl peroxide, other organic peroxides such asditertiary butyl peroxide, t-butylhydroperoxide, ultraviolet light andionizing radiation. The preferred free radical initiators areultraviolet light and ionizing radiation given off by radioactiveisotopes, and combinations of ultraviolet light and ionizing radiation,for the reason that they induce little polymerization and do not add anyextraneous materials which may have an effect on subsequent separationof ingredients.

The reaction between the unsaturated compounds and thel-ha1o-3-mercapto-2-propanol can be shown generically as free radicalinitiator R CH1=CH1 X-CHz-CHOHCHzSH where R, X and n are the same asdefined above. It is to be understood that the olefinic group of thereactant need not be terminal, although the latter are considerably morereactive, in general, than internal olefinic groups.

The examples which follow are intended to illustrate the invention, butnot limit it. All parts are by weight unless otherwise specificallyindicated.

DETAILS OF DISCLOSURE Hydrocarbon Derivatives. Aliphatic Example 1 A 600ml. beaker fitted with a magnetic stirrer and immersed in a water baththrough which cooling water was circulated, was charged with 0.5 mole of1-chloro-3- mercapto-Z-propanol and 0.5 mole of octene-l was addeddropwise. The beaker was irradiated with an UA-Z ultraviolet ray lamp.The temperature was maintained at about 20-30 for 1 hour. At thebeginning of the reaction period, two immiscible layers were apparent.However, after about 15% of the olefin reacted with the l-chloro-3-mercapto-2-propanol, the mixture became completely miscible.

The mixture was then separated by distillation. The fraction boiling at118-119 C. at 0.1 mm. Hg was found to be C H S-CH CH OHCH CL It had arefractive index at 25 C. of 1.4828. On analysis it was found to contain56.48% C, 10.08% H and 13.69% C1. The yield based on the olefin wassubstantially quantitative.

Examples 2-4 TABLE I B.P., Moles Hrs. U.V. Percent Deg. 0.] Ex. OlefinUMP/olefin exposure yield 0.2 mm. no

2.---. CIOHZB 1. 25:1 1. 75 91 137-7 1. 4840 3. CsHn 1. 25:1 7 80 826 1.4901 4--- GH10 1.511 1.67 79 72-3 1. 4932NorE.-CMP=1-chloro-3-mercapto-2-propanol.

These data show that good yields of the adduct can be obtained witholefins having terminal or non-terminal unsaturation. With some olefinshaving non-terminal unsaturation, it is necessary to carry on thereaction for a longer time than with terminal olefins. However,pentene-2 reacted about as fast as a terminal olefin.

The alkene which can be reacted with the chloromercaptopropanol cancontain from 2 to about 24 carbon atoms.

With alkadienes, usually a mixture of monoand diadduct is formed,although the diadduct can be formed to the substantial exclusion ofmonoadduct if an excess of halomercaptopropanol is employed for fairlylong reaction periods. Best yields of mono-adduct are obtained by usingan excess of diolefin and slow addition of the 1-chloro-3-mercapto-propanol-2 to the diolefin. In some instances, it isdesirable to employ a common inert solvent for the diene andchloromercapto propanol to assure that a single phase is present duringthe entire reaction period.

Example 5 An 800-ml. beaker cooled with external cooling coils wascharged with 1.5 moles of 1,5-hexadiene and 35 g. of isopropyl alcohol.The mixture was stirred with a magnetic stirrer and irradiated with aUA-2 ultraviolet lamp while adding 1.5 moles of l-chloro-3-mercapto-2-propanol over a period of 3.75 hours. The mixture was thereafterirradiated for 3.5 additional hours, using a C0 source. The mono-adduct'was flash distilled from the mixture at a temperature of about 105 C.at 0.1 mm. and then redistilled through a fractionating column at -97 C.and .1 mm. pressure. The colorless liquid weighed 69 g. The residue fromthe flash distillation was diadduct. When this reaction was repeatedwith a ratio of 4 moles of the chloromercaptopropane with 1 mole of thediene and a reaction time of 7 hours, a 74% conversion of the diene tothe diadduct, which had the structure ClCH CHOHCH S(CH SCH CHORCH Cl,

was obtained.

Example 6 The procedure of Example 5 was repeated using 1 mole of1,7-octadiene and 1 mole of 1-chloro-3-mercapto-2- propanol. Themonoadduct after flash distillation and redistillation through afractionating column weighed 70.2 g.

Repeating this run with 2 moles of the chloromercaptopropanol with onemole of 1,7-octadiene and a reaction time of three hours resulted in a97% yield and 84% conversion of the diene to the diadduct.

Example 7 A mixture of 1-chloro-3-mercapto-2-propanol and butadiene in amolar ratio of 2 to 1 was exposed to ultraviolet light for hour at atemperature of 5 to 20 C. The yield of 1,4 monoadduct was 35%. It had aB.P. at 0.2 mm. of 71-73 and a refractive index of 1.5169.

In order to obtain best yields with gaseous olefins, it is preferred toadd the olefin to the chloromercaptopropanol under sufficient pressureto maintain the olefin in a liquid state at a temperature of about 1030C.

The monoadducts of the dienes can be used as comonomers with alkadienesor polymerizable monoolefinic compounds to provide copolymers havingvery reactive side chains.

ALKENECYCLOHEXENES Example 8 A mixture of 21.6 g. of 4-vinyl cyclohexene(0.2 mole) and 25.2 grams (0.2 mole) of 1-chloro-3-mercapto-2- propanolin an externally cooled beaker to maintain the temperature at 20-25 C.,was irradiated for 5.5 hours with a UA-2 ultraviolet lamp. Stirring wascontinued during the irradiation period. Flash distillation of thereacted mixture yielded 24.3 g. of monoadduct boiling at 132-144" C. at0.1 to .15 mm. pressure. The refractive index was 1.5302. Analysis onthe monoadduct fraction by nuclear magnetic resonance indicated that theproduct was about a 3 to 1 mixture of CH CH S CHICK] O HCH: Cl andClHzCCHrOHCHz-SQ Analysis of the mixture showed that it contained 56.5%C and 15.28% C1. The calculated values for the monoadduct are C 56.27%and Cl 15.10%. V

The residue in the distillation vessel weighed 13.5 g. It was thediadduct CH CHgS CHzCHa O HCH: C l

ClHzCCHzOHCHz-S H j 6 Example 10 The reaction of1-chloro-3-mercapto-2-propano1 with dicyclopentadiene in a molar ratioof 2.2 to 1, respectively, for 2% hours at approximately roomtemperature with UV irradiation resulted in complete conversion of theolefin. About 58% was the diadduct and 42% was monoadduct. Themonoadduct boiled at 137-144 at 0.1 arm, n;, 1.5556 while the diadductremained as a pot residue.

Example 11 A mixture of 1.5 cyclooctadiene and1-chloro-3-mercapto-2-propanol in a molar ratio of 1 to 2.4,respectively, was exposed to ultraviolet radiation for five hours atapproximately room temperature. It was found that about 92% of the dienewas reacted and the conversion to the monoadduct was 65%. The exactstructure of the diadduct formed was not determined, since twopositional isomers each could exist as cis-trans pairs.

By substituting 1,3-cyclooctadiene for the 1,5 isomer and using anirradiation period of 14 /2 hours, a 91% yield with a 76% conversion tomonoadduct was obtained. The 1,2- and 1,4-monoadducts were obtained aswell as a diadduct of unidentified structure.

The monoadducts of the cyclic dienes can be employed in the same manneras the monoadducts of the alkadienes.

TERPENE AND B-ICYCLOALKENE DERIVATIVES Example 12 Terpene hydrocarbonsand bicycloalkenes also react with l-chloro-3-mercapto-2-propanol toform adducts. Tabulated below are results obtained with certainrepresentative bicycloalkenes or terpene compounds. In all cases, theruns were made at about room temperature.

The reaction of 1,2,4-triviny1cyclohexane with thechloromercaptopropanol in a molar ratio of 1 to 2, respectively,produces a mixture of the triadduct, monoadduct, and isomeric diadducts.

In another example, 202 g. (1.6 moles) of 1-mercapto-3-chloro-2-propanol was charged to a 500 ml. three neck flask fittedwith stirrer, condenser, nitrogen sparge and dropping funnel. A solutionof 1.31 g. (0.008 mole) of azobisisobutyronitrile in 65 g. (0.4 mole) of1,2,4-trivinylcyclohexane was added to the mercaptan at 70 during threehours. After heating for two hours longer, an additional 1.31 g. ofcatalyst was added, and heating continued for an additional seven hours.The crude product was charged to a flash still and 81 g. of unreactedmercaptan removed by heating to 120 at 0.5 mm. The net weight of theproduct was 180 g. corresponding to 0.91 mole of mercaptan reacted or anaverage of 2.3 double bonds reacted.

CYCLOALKENES' Example 9 A mixture of a 2:1 molar ratio ofchloromercaptopropanol to cyclopentadiene was exposed to ultravioletlight for two hours at room temperature. About 26% of the diene reactedto form the monoadduct and 14% formed the diadduct.

CH1SCH1CHOHCH:C1 and ClCHzOHOHCH S- =CH1 while the nortricyclenestructure is probably CH2 S CH2 1 HCHnl In place of the naturallyoccurring dl-dipentene, one may also use the pure d-isomer, d-limonene.Either of these substances can form a monoadduct of the structure CH; CHS CHnCHOHCHzCl 7 8 2,2,1-bicycloheptadiene is capable of forming twoWhen highly polymerizable olefins such as styrene, pmonoadducts. Thestructure of these is shown by nuclear chlorostyrene, or vinyl chlorideare utilized, the product magnetic spectroscopy to be a mixture of willconsist of telomers in addition to the 1:1 adduct.

These telomers have the general formula & scmcnoncmoi and somononcrnolThe latter isomer is favored by a low mercaptan to olefin ratio whilethe former isomer is favored by a high mer- 10 captan to olefin ratio.Since at high mercaptan to olefin ratios diadduct may be formed, toobtain maximum yields where R is phenyl, chloro, or cyano and n is aninteger up of the unsaturated monoadduct, the reaction must be to aboutfive. Formation of 1:1 adduct is favored by high stopped at lowconversion. mercaptan to olefin ratios, while telomerization is favoredOther terpenes reacted with obtainment of good yields by low mercaptanto olefin ratios.

of adduct:

Example 14 Terpene Product formed Alpha plnene CH;

Polyolefinically substituted aromatic compounds can be also reacted toform derivatives in which part or all of the olefinic substitutents aresaturated. Thus, if it is s-CHCHoHCHm desired to retain any degree ofunsaturation in the adduct, the amount of halomercapto propanol added isadjusted to less than the stoichiometric amount needed to saturate theolefinic substituents on the aromatic rings. If saturation of theolefinic bonds is desired, it is preferred to employ an appreciableexcess over that stoichiometrically required, because the additionreaction does not always go to completion with merely molar equivalentsof olefinic unsaturation and the halo-mercapto a1- cohol. on, Ingeneral, the polyadducts are high boiling materials g ggogcms which aredifficult to distill. However, flash distillation OH; is elfective forremoving any unreacted halo-mercapto propanol and in many instances, themonoadduct.

If unsaturation remains on the aromatic compound,

Beta plnene (EHzSCHzCHOHCHaCI 25 other tefpenes which can be reactedInclude typical examples of which are allyl or isopropenyl groups, Phenesubmene d'fenchene p'fenchene' and fi'phenan' the adduct can behomopolymerized or copolymerized drenewith other unsaturated compoundsby known techniques. AROMATIC S TUT OLEFINS 40 Alternatively, thehalohydrin group of the adduct can be converted to an epoxide. Theepoxide can be homoor Example 13 copolymerized. Homopolymers andcopolymers obtained Typical aromatic substituted monoolefins used toexemfrom the adducts have reactive OH and halogen groups plify theinvention are styrene, alpha methyl styrene and in the side chains whichcan be used for crosslinking purp-ethyl styrene. It is understood thatthe aromatic portion poses and for the formation of derivatives. of themolecule can contain any other substituents which Listed below arerepresentative polyolefinically-substiare non-reactive with thehalomercapto propanol. Repretuted aromatic compounds which can bereacted to form sentative substituents are halogen, alkyl, carboxy,ester, adducts with l-mercapto-3-halo-2-propanol. In the first sulfone,cyano, nitro and tertiary amino groups. The arofour runs, Co was theirradiation source, and in Run matic group can be mono or polycyclic andthe latter can 5, an ultraviolet light source was employed as thecatalyst. be fused or non-fused. The first run was exposed to 5 megaradsof Co radia- The procedure employed for reacting alpha-methyltion andRuns 2-4 each was subjected to 3 megarads. The styrene was to permit themixture of reactants to stand mixtures which were exposed to Co wereplaced in a for two weeks at room temperature before work-up. Allcitrate bottle, the air was replaced with nitrogen and the othermixtures were exposed to ultraviolet light for short 55 bottles werecapped before irradiation. Run 5 was run at periods of time. roomtemperature in a beaker.

TABLE III Mole ratio CMP/ Hrs. U.V. Percent; B.P.,C. Olefin olefinexposure yield per mm. m)

.5 lf&;aas::::::: 321 3?. 135% 1.52%

Halogenated hydrocarbons can be readily reacted by the same procedure asthat described above. Representa- TABLE IV tive reactants are vinylchloride, allyl chloride, the butenyl M chlorides, allyl fluoride,1,1,2-trifluoro-2-chloro-ethylene, 5g Olefin g 52g;1,1,2-trifluoroethylene, 3,3,3-trifiuoro-1-propene and p- 1l-allyloxy-Z-methoxy-4-a1ly1benzene 2:1 chlorostyrene- 21,2-diallyloxybenzene 2:1 In the examples below, the procedure followedwas that a-.. l-allyloxy-2-allylbenzene described in Example 1. Theconversion of mercaptan to g: gfg glgg figfiffi'gfiggkg ti h d ve aNorm-GM]?=l-chloro-B-mercapto-Z-propancl.

Yields of the above adducts are generally above 80%. In Run 5, only twoequivalents of mercaptan were used for four equivalents of unsaturation,so the product will contain, on an average, two sites of unsaturation.

When p-divinyl benzene was added to a 2 mol ratio quantity ofchloromercaptopropanol over a period of 20 minutes and irradiated forhours with ultraviolet light, a mixture of compounds was obtained,including one or more telomers having more than 1 divinyl benzene unitfor each two chlorohydrin groups. The actual structure of the telomerswas not determined. The data showed that about 85% of thechloromercaptopropanol reacted. In two additional runs 132 g. of thedivinyl benzene were reacted, respectively, with 126.5 g. and 190 g. ofchloromercaptopropanol. In each case the conversion of olefin wascomplete. In the former case the chloromercaptopropanol was allconverted, while in the latter case only a small amount was unreacted.

Diisopropenyl benzene reacts with chloromercaptopropanol in a mannersimilar to divinyl benzene. The example 0.3 mole of m-diisopropenylbenzene was reacted with 0.6 mole of the chloromercaptopropanol thereaction was carried out in 100 ml. propanol at a temperature of 60 C.for 50 hours without catalyst.

Other polyolefinically unsaturated aromatic compounds which readilyundergo addition of halomercapto propanol are:

OCHgCH=CH2 CH CHCIEHOQO CHzCH=CHa CHzCH=CHn CHFCHCH CHgCH=CHz 0CHnCH=CH3 H: C H= C H:

CH: 0 ----CH: C H=CH9 where n=1 to 4 CH OH=CHz 10 Any compound havingthe structure (CH =CHCH .Ar(0CH CPI=CH when n=0-2 and x=1-3 and Ar isaromatic, haloaromatic or aralkyl can be used.

UNSATURATED ALIPHATIC ALCOHOL AND ETHER DERIVATIVES Example 15 Thisexample shows that alcohols and ether-alcohols having aliphaticunsaturation can be reacted with l-mercapto-3-halo-2-propanol to formadducts having thioether and halohydrin groups.

The unsaturated alcohols can have more than one OH group and can bemonoor polyunsaturated. Acetylenic and olefinic alcohols can be reactedto form adducts. Acetylenic compounds can add two moles of the mercaptohalopropanol. Alcohols having from 3-16 carbon atoms can be reacted, butthe preferred carbon length of the alcohols is from 3 to about 12.

Run 1: To one mole of l-mercapto-S-chloro-2-propano1 one mole of allylalcohol was added over a period of about an hour. The mixture wasstirred and exposed to ultraviolet light during this time. Irradiationand stirring was continued for an additional ten hours. The crudeproduct was charged to a flash still and unreacted ingredients wereremoved at C. and .2 mm. pressure. The residue contained 18.9% C1 and18.7% S. It had the structure CICH CHOHCH S (CH CH OH.

Run 2: A solution containing .25 mol l-hexane-3-ol and .25 mol ofl-mercapto-3-chloro-2-propanol in 100 ml. isopropanol was subjected to3.6 megarads of radiation from a Co" source. Thereafter the solution wastransferred to a breaker and subjected to ultraviolet light for eighthours. Analysis of the solution by vapor phase chromatography showedthat essentially all the reactants were converted.

The sulfur was found to be attached to the terminal carbon atom. Theadduct had the structure CH (CH CHOH (CH SCH CHOHCH Cl Run 3: In thisrun 4-hexene-3-ol was substituted for the terminally unsaturated hexenolof Run 2. Otherwise, the procedure was identical to that described inRun 2. After completion of the irradiation, the mixture was heated to100 C. at .3 mm. to remove the solvent and unreacted ingredients. It wasfound by nuclear magnetic resonance spectroscopy to consist of a mixtureof CH CHz C H O H C HCHzCH;

Hz 0 H and CH CHz C H O HCH: C HCH:

Run 4: An equimolar mixture of 2-ally1-2-ethyl-1,3- propanediol and1-mercapto-3-chloro-2-propanol in 50 ml. isopropanol was subjected toirradiation by the procedure described in Run 2. The reacted mixture wasflash distilled at C. and .2 mm. pressure to remove the solvent andsmall amounts of unreacted ingredients. Its structure was C H C (CH OH)(CH SCH CHOHCH CI Run 5: In this run, equimolar quantities of undecenylalcohol and 1-mercapto-3-chloro-2-propanol were irradiated with Co untilthe total dose was 2.0 megarads. The

1 1 product obtained was a white waxy solid. It had the structuremCHgOH.

Run 6: A citrate bottle was charged with 0.2 mole of propargyl alcoholand 0.4 mole of 1-mercapto-3-chloro- 2-propanol, flushed with nitrogenand sealed. It was exposed to 3 megarads of radiation from a C source.The crude product was dissolved in chloroform and extracted with 1.5 NNH OH to remove small amounts of unreacted mercaptan. The solution wasthen washed with four portions of water, dried and the CHCl wasevaporated. The product contained 34.2% C, 24.6% C1 and 22.4% S. Themolecular weight by boiling point elevation was 291 as compared to acalculated molecular weight of 308 for the diadduct. The product was amixture of CH: ClCHzCHOHCHzSC=CHCH2OH, ClCHzCHOHCHzSii-CHzOH and CHCHzOHCH2 CH2 HOH HOH with the latter predominating:

Other representative unsaturated alcohols which react withchloromercaptopropanol are 3,5 dihydroxy 1- pentene, 3-hydroxy 1heptene, 1,4-dihydroxy-2-butyne. The latter can add 1 or 2 moles of thechloromercaptopropanol to form compounds with the structureHOCHzC=CH-CH:OH and HOCHaCH-CH-CHzOH l l l 2H; ('ZH; 2H: JJHOH HOH HOH(5H; Cl H2 Cl Hz Cl UNSATURATED ETHER ALCOHOLS Molar ratio 01' Runalcohol number Ether alcohol to CMl 71-allyloxy-2,2-bis(hydroxymethyl)butane 1:1 8l,3-bis(allyloxy)-2,2-di(hydroxymethyDpropane- 1. 2:1 92,2-bis(allyloxymethyD-l-butanol 1:2 10 1-allyloxy-3-chloro-2-propano11:1 11 1-allyloxy-2-(1-chloro-2-hydroxypropoxy) propane- 1 1 121-allyloxy-2,2-bis(hydrcxymethyl)propane 1 :1 13- 1,3-bis(a1lyloxy)-2-hydroxymethyl-2-ethyl propane- 2:1 14." 2 allyloxy ethan 1:1 152-vinyloxy ethanol-1- 1:1 16 Monoallyl ethers of oly(ethylene glycols)having 1:1

about 10 and 12 HzCHzO) units in the chain. 17 Monoallyl ethers ofcopolymers of ethylene and 1:1

propylene oxides having molecular weights of about 200 to 1,000. 18Allylglycidyl ether/propylene oxide copolymer 1.5:1

adouble bond equivalent weight about 353) in isopropanol solution.

The yields of adducts in the above examples were generally nearlyquantitative.

Example 16 Monoand polyunsaturated ethers and thioethers can be reactedwith 1-merca pto-3-halo-2-propanol to form addducts with polyunsaturatedethers, polyadducts or mixtures of monoand polyadducts can be formed.The ethers can be open-chain or cyclic.

Run 1: A citrate bottle containing .22 mole of 1,2-di- (allyloxy) ethaneand 0.4 mole of 1-mercapto-3-chloropropanol-2 dissolved in 100 ml.isopropanol was subjected to 3.4 megards of radiation from a C0 source.The solution was transferred to a beaker in a cool water bath andstirred. An additional 10.1 parts of the mercapto halopropanol wereadded and the solution was irradiated for ten hours with an ultravioletray lamp. The resulting product was the diadduct of the diallyoxyethane.

Run 2: A solution of 0.1 mol 1,4-diallyloxy-butene-2 and 0.3 mole of1-mercapt'o-3-chloro-propanol-2 in 100 ml. isopropanol was subjected to3.4 megarads of radiation from a C0 source and subsequently exposed toultraviolet light for 8 hours. Unreacted ingredients were removed byflash distillation. The sulfur content of the reaction productcorresponded to a diadduct.

Run 3: When diallyl ether is employed as a reactant the end productobtained can be either a diadduct of the mercapto halopropanol or amixture of monoadduct, diadduct and a cyclic ether adduct.

Run 4: To a beaker containing 0.6 mole of l-mercapto-3-chloro-2-propanol which was irradiated with ultraviolet light wasadded 0.2 mol of diallyl ether dropwise over a period of about 20minutes. The mixture was irradiated for about 1.3 hours after adding thediallylether. Stirring was continuous during the entire process. Thecrude product was flash distilled at and .15 mm. leaving an 88% yield ofthe diadduct. To obtain good yields of the diadduct, themercapto-halo-propanol should always be present, preferably in fairlylarge excess as compared to the diallyl ether.

Run 5: To one mole of diallyl ether, irradiated with ultraviolet light,one mole of 1-mercapto-3-chloro-2- propanol was added dropwise over aperiod of two hours. The crude product was flash distilled at 80 C. and.15 mm. The distillate consisted of GRIT-0113s CHzCHz O HCH: C1

while the distillation residue was mainly diadduct. When dimethallylether is substituted for diallyl ether, the cyclic ether formed by thisprocedure has the structure and CHlSCHlOHCHjCl ture USCH -CHzOHCIhCl Run7: Reaction of one mole of allyl glycidyl ether with 2 moles ofchloromercaptopropanol forms essentially of a product with the structureCICH CHOHCH S (CH OCH CHOHCH SCH CHOHCH CI This reaction was carried outunder ultraviolet light irradiation for 3 /2 hours. In another run .05mole of was reacted with .1 mole of chloromercaptopropanol at autogenoustemperature for three days. Analysis showed that 88% of the epoxy groupswere reacted and only a trace of unsaturation remained. The compoundformed had the structure where Z is 3 il or Srand A is the remainingresidue of the carboxylic or sulfonic acid. In general, the cyclicadduct 18 formed in CICHZCHOHCHZSC2H4SC2H4OCH2 preference to the openchain adducts unless a large ex- CHOHCHZSCHZCHOHCHZCI cess of mercaptanis used. EXAMPLE 17 The double bond in the acid portion of unsaturatedamides such as those derived from undecyl amide, 2,2,1- A typlcalrepresentatlve of uniaturated esters whlphbicyclohept-S-ene-Z-carboxylic amide, or 4 cyclohexenereact withmercapto halopropanol 1S allyl acetate. A lTllX- carboxamide are alsoreactive ture of 85% purity allyl acetate and 1-mercapto-3-chloro-2-propanol in a mole ratio of 1 to 2 was allowed to stand UNSATURATEDACETALS overnight. The mixture was fractionally distilled and a fractionboiling at 126-127 C. and 0.1 mm. pressure was 52: :32 ggg g ffiz gi iggalcohol and propane obtained in an 92% yield. This fraction had arefractive index at f (CH =CHCH O )CHCH CH(OCH CH=CH;,)

When purified allyl acetate as a reactant was substituted was reacted ih 4,0 mhles of 1 3- .z. for the 85% material and the mixture wasirradiated With anol by using C060 as a free radical initiator Theprodultraviolet light for 31/2 hours, the Yield of Purified not obtainedfrom this reaction was a viscous brown terial, obtained as describedabove was 82%. This fracli id, tion had a refractive index of Otherrepresentative acetals which can be reacted to )ther unsaturated esterswhich were reacted in a mole fo adducts with the above d fin dmercaptohaloproratio of 2 MC? to 1 of ester to term adducts with 1- anelinclude but are not limited to the allyl alcohol p 'P P are i Ylsopqthfllate acetals of acetaldehyde, propionaldehyde, benzaldehyde,100% reacted under 3 megalads dlallyl male acrolein, methacrolein,4-cyclohexeny1 aldehyde, the ate, diallyl adipate,di(4-cyclohexenyl)methyl succinate aldehyde (10 hours exposure toultraviolet light, 72% yield of brown liquid), diethylene glycolundecylenate (about 10 2 hours U.V. radiation, 59.6% yield of brownliquid), triallyl trimesate, \H

CO0(CH:)z0OC- 0112020 1 Addition may occur at the double bond of theallyloxy 5 group, or addition can also take place at other sites ofunsaturation such as those in acetals of acrolein and 4- cyclohexenealdehyde. Example 18 From the above it is apparent that R of the genericIn this example, representative compounds having one formula can bederived from the alcohol moiety of C C or more aliphatically unsaturatedhydrocarbon groups alcohols having 1 to 2 OH groups and can contain anattached to a nitrogen atom are employed as one reactant olefinic group.with a mercapto halopropanol. In all instances, the reac- The residue ofthe ether alcohols can contain from 4 C tions were catalyzed byultraviolet light. Listed below are atoms up to that derived from amonoallyether of a polythe compounds reacted with1-mercapto-3-chloro-Z-proallylene glycol of molecular weight up to about1000 and panol, the mol ratios of reactants, the reaction period canhave from 2 to 3 C atoms in the allylene groups. and the yieldsobtained. The residue of the ethers in the R group can contain TABLE VIM01 ratio Run MOP] U.V., Percent No. Olefin olefin hrs. yield 1N,N,N',N-tetraal1ylterephthalimide 4 2.. N,N-dially1 acetami e-.- 3-.N,Ndiallyliormamide. 4.- N,N-diallyl 3-buteneoieac 5.- N,N-dially1undecy1amide 6 N,N,N,N'-tetrallyladlpamide 7 N,Ndially1 benzamide 8N,N-dially1 GON= 9 N,N-diallylbenzenensu1fonamide 2:1 3 N-allylsuccinimide 2:1 2% 11 N-allyl 1,2-dicarboxy-4-eyclohexeneimide 2:1 7% 8112 Triallylcyanurate 4:1 13% 38 3.5 megarads from a Cow source. bDiadduet.

N,N-diallylamides and N,N-diallylsulfonamides in addition to forming theexpected diadduct may form two monoadducts. In addition to the expectedopen chain monoadduct, a cyclic monoadduct of the type 6 to -10 C atoms,1 to 2 olefinic groups of 3 C atoms each or it can be derived from2,5-dihydrofurane.

We claim:

1. A compound of the structure CHaCH-CHCH SCH:CHOHCH:C1

H: H, wherein n is 1 to 2 and X is selected from chlorine or bromine andR is a hydroxylated hydrocarbon residue |A of a 0 -0 unsaturatedaliphatic alcohol said residue z 75 having from 1 to 2 OH groups and upto 1 olefinically un- 15 saturated group, the residue of an unsaturatedunsubstituted aliphatic ether alcohol having from 4 C atoms topolyalkylene glycol monoallyl ethers having a molecular weight up to1000, said polyalkylene glycol monallyl ethers having from 2 to 3 Catoms in the alkylene groups, the residue of an olefinically unsaturatedunsubstituted linear ether said ether having 1 to 2 olefinic groupshaving 3 C atoms each and a total of '6 to 10 C atoms a C monoolefinicmonohydric alcohol and n is 1.

5. A compound of claim 1 having the structure CHwCHCHzOH HOH E011 E101HaCl 1 6 6. Compounds of claim 1 in which R is the residue of adiallylether of a mono or dihydric alcohol, said residue containing 8 to12 C atoms and n is 1 to 2.

7. Compounds of claim 1 in which R is the residue of a monoallyldihydric alcohol 8-9 C atoms and n is 1.

8. A compound of claim 1 having the structure CH CICHOHCH O (CH3SCH2CHOHCH2C1.

9. A compound of claim 2 having the structure CH ClCHOHCH S(CH O(CH SCHCHOHCH Cl.

10. A compound of claim 1 in which R is a propargyl alcohol residuecontaining one SCH CH0HCH Cl.

References Cited Todsen: J. Amer. Chem. Soc., vol. 72 (1950), pp.4000-4002.

LEWIS GOTIS, Primary Examiner D. R. PHILLIPS, Assistant Examiner U 5.Cl. X.R.

260-3472, 609 E, 459.5, 248 FS, 326 H, 535 H, 556 AR, 557 B, 558 S, 561S, 609 F

